Biomass Sucrose‐Derived Cobalt@Nitrogen‐Doped Carbon for Catalytic Transfer Hydrogenation of Nitroarenes with Formic Acid

Abstract

Fabrication of non‐noble metal‐based heterogeneous catalysts by a facile and cost‐effective strategy for ecofriendly catalytic transfer hydrogenation (CTH) is of great significance for organic transformations. A cobalt@nitrogen‐doped carbon (Co@NC) catalyst was prepared from renewable biomass‐derived sucrose, harmless melamine, and earth‐abundant Co(AcO)2 as the precursor materials by hydrothermal treatment and carbonization. Co nanoparticles (NPs) were coated with NC shells and uniformly embedded in the NC framework. The as‐obtained Co@NC‐600 (carbonized at 600 °C) catalyst exhibited excellent catalytic efficiency for CTH of various functionalized nitroarenes with formic acid (FA) as hydrogen donor in aqueous solution. The uniformly incorporated N atoms in the C matrix and the encapsulated Co NPs showed synergistic effects in the CTH reactions. A mechanistic analysis indicated that the protons from FA were activated by Co sites after being captured by N atoms, and then reacted with nitroarenes adsorbed on the surface of the catalysts to generate the corresponding aromatic amines. Moreover, the catalyst showed excellent durability and reusability without obvious decrease in activity even after five reaction cycles. Thus, the study reported herein provides a cost‐effective, sustainable strategy for fabrication of biomass‐derived non‐noble metal‐based catalysts for green and efficient catalytic transformations.

Production of γ‐Valerolactone from One‐Pot Transformation of Biomass‐Derived Carbohydrates Over Chitosan‐Supported Ruthenium Catalyst Combined with Zeolite ZSM‐5

“…Based on the experimental details and previous literatures,[29b], [29c], we proposed a possible reaction mechanism for the above‐mentioned one‐pot FF conversion to GVL (Scheme ). It is noted that both Ru 3+ ions and N atoms in the chitosan‐Ru can serve as the possible active catalyst sites.…”

Preparation and Performances of ZIF-67-Derived FeCo Bimetallic Catalysts for CO2 Hydrogenation to Light Olefins

“…The lower pyrolysis temperature led to a very low degree of graphitization of the support NC layer, and no graphitic nitrogen was found in FeCo/NC-400 ( Figure 8a). As the temperature reached above 500 • C, the graphitization degree of the support increased and a small amount of graphitic nitrogen began to form (Figure 8b-d) [61]. The presence of nitrogen can provide anchor sites, which promotes high dispersion of the metal [40].…”

Cobalt Entrapped in N,S‐Codoped Porous Carbon: Catalysts for Transfer Hydrogenation with Formic Acid

“…[3][4][5][6][7][8] However,t hese processes are limited by specialized reaction equipment,l ow selectivity,a nd potential safetyi ssues regarding hydrogen storage and transportation. In this respect, it is essential to develop as afe, clean, highly selective, and efficient process for the reduction of nitroarenes.C atalytic transfer hydrogenation (CTH) has been considered as ac andidate for reduction of nitroarenes with hydrogen donors, such as HCOOH( FA), [9,10] N 2 H 4 ·H 2 O, [11] NH 3 ·BH 3 , [12] andN aBH 4 . [13] Among them, FA is almosta ni deal candidate for CTH because of its nontoxicity, convenience, and recyclability.…”